EP0789043B1 - Polyurethan-Pulvermattlacke - Google Patents
Polyurethan-Pulvermattlacke Download PDFInfo
- Publication number
- EP0789043B1 EP0789043B1 EP97101185A EP97101185A EP0789043B1 EP 0789043 B1 EP0789043 B1 EP 0789043B1 EP 97101185 A EP97101185 A EP 97101185A EP 97101185 A EP97101185 A EP 97101185A EP 0789043 B1 EP0789043 B1 EP 0789043B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- component
- carboxyl
- blocked
- coating powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000576 coating method Methods 0.000 title claims description 92
- 239000000843 powder Substances 0.000 title claims description 78
- 239000004814 polyurethane Substances 0.000 title description 16
- 229920002635 polyurethane Polymers 0.000 title description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 48
- 229920001228 polyisocyanate Polymers 0.000 claims description 31
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 30
- 239000005056 polyisocyanate Substances 0.000 claims description 30
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 150000008064 anhydrides Chemical class 0.000 claims description 17
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 239000002981 blocking agent Substances 0.000 claims description 8
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic hydroxycarboxylic acids Chemical class 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000002076 thermal analysis method Methods 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical class O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 16
- 239000004971 Cross linker Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 229920002732 Polyanhydride Polymers 0.000 description 10
- 238000004455 differential thermal analysis Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- AGJCSCSSMFRMFQ-UHFFFAOYSA-N 1,4-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(C(C)(C)N=C=O)C=C1 AGJCSCSSMFRMFQ-UHFFFAOYSA-N 0.000 description 3
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 2
- YJCJVMMDTBEITC-UHFFFAOYSA-N 10-hydroxycapric acid Chemical compound OCCCCCCCCCC(O)=O YJCJVMMDTBEITC-UHFFFAOYSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N 12-hydroxylauric acid Chemical compound OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- ZTXDHEQQZVFGPK-UHFFFAOYSA-N 1,2,4-tris(oxiran-2-ylmethyl)-1,2,4-triazolidine-3,5-dione Chemical compound C1OC1CN1C(=O)N(CC2OC2)C(=O)N1CC1CO1 ZTXDHEQQZVFGPK-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- IINXALNHMRMYDC-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O.OC(=O)CCCCCCCCCCC(O)=O IINXALNHMRMYDC-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- RRBRFYNWESTLOL-UHFFFAOYSA-L hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC([O-])=O.CCCCCC([O-])=O RRBRFYNWESTLOL-UHFFFAOYSA-L 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PULCKIYKBGOTTG-UHFFFAOYSA-N n-(2,4-dimethylpentan-3-ylidene)hydroxylamine Chemical compound CC(C)C(=NO)C(C)C PULCKIYKBGOTTG-UHFFFAOYSA-N 0.000 description 1
- UCFRVQXGPJMWPG-UHFFFAOYSA-N n-(2,6-dimethylheptan-4-ylidene)hydroxylamine Chemical compound CC(C)CC(=NO)CC(C)C UCFRVQXGPJMWPG-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/934—Powdered coating composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the invention relates to a powder coating for the production of matt coatings.
- Powder coatings do not pose any harmful effects when applied Solvent-free, can be processed with a very high degree of material utilization and are therefore considered to be particularly environmentally friendly and economical.
- thermosetting powder coatings based on polyurethane.
- the today Polyurethane (PUR) powder coatings established on the market generally consist of solid polyester polyols with solid aliphatic or cycloaliphatic Polyisocyanates, generally cured in blocked form.
- Polyurethane powder coatings that cure reproducibly to matt coatings, you get e.g. according to the teaching of DE-A 338 129 from polyester polyols and ⁇ -caprolactam-blocked Polyisocyanate crosslinking agents based on isophorone diisocyanate (IPDI) with simultaneous addition of the high-melting pyromellitic dianhydride (Mp: 284-286 ° C). Powder coatings with low Degree of gloss also results if polyester polyols are blocked with special ⁇ -caprolactam Derivatives of trans-1,4-diisocyanatocyclohexane with a Melting range above 140 ° C, e.g.
- DE-A 3 711 374 are, or with polyaddition compounds based on IPDI uretdione polyisocyanates with melting points above 130 ° C, preferably above 140 ° C, as they are available according to the teaching of DE-A 3 328 133 combined become.
- the powder coatings of these publications have in common that they each have a Contain reaction components that have a melting point significantly above that at the production of powder coatings usual extrusion temperatures (in general 80 to 120 ° C).
- the achievable matt effects are based on all Cases of insufficient mixing of the reactants during the Melt extrusion. Because of the inhomogeneities in the paint powder have the coatings obtainable with the aid of the powder coating systems mentioned usually only moderate paint properties.
- powder coatings result from a mixture of two Hydroxyl polyesters with different OH numbers and reactivity in combination with commercially available IPDI-based, non-releasing uretdione powder coating crosslinkers also matt polyurethane covers.
- this procedure is based on the Limited use of very special polyester polyols and not easily transferable to any binder.
- the powder coatings according to the invention are based on the surprising observation that polyurethane powder coatings, consisting of a Polyester polyol and a blocked powder coating crosslinker containing isocyanate groups, which generally burn into glossy lacquer films, completely matt coatings result when the formulation is additionally combined from a carboxyl and / or carboxylic acid anhydride groups Crosslinker component and another against carboxyl and / or carboxylic anhydride groups crosslinker component having reactive groups added and all components homogenized by melt extrusion.
- powder coatings consisting of a polyester polyol, a blocked polyisocyanate and only one further, for example only one Crosslinker component having carboxyl and / or carboxylic anhydride groups or only one versus carboxyl and / or carboxylic anhydride groups reactive crosslinker components deliver high-gloss coatings, and also the combination of a carboxyl and / or carboxylic anhydride group having and one against carboxyl and / or carboxylic anhydride groups component having reactive groups on its own gives a shiny film.
- Harden powder coatings according to the invention to matt surfaces in particular also not because it is known that the addition of a combination of one high molecular weight carboxyl group-containing powder coating binder and one component reactive with this binder, for example one Polyepoxide crosslinker, also a glossy finish for a polyurethane powder coating provides curing coating material.
- the invention also relates to the use of this powder coating for Coating of any heat-resistant substrates.
- component A) contained in the powder coatings according to the invention it concerns any hydroxyl groups known from powder coating technology containing binders with a hydroxyl number of 25 to 200, preferably from 30 to 150, a medium (from the functionality and the Predictable hydroxyl content) molecular weight of 400 to 10,000, preferably from 1000 to 5000, which are solid below 40 ° C and liquid above 130 ° C are.
- Such binders are, for example, hydroxyl-containing polyesters, polyacrylates or polyurethanes, such as z. B. in EP-A 45 998 or EP-A 254 152 are described as powder coating binders, but also any Mixtures of such resins.
- Component A) is preferably hydroxyl-containing Polyester, its softening temperature - determined according to differential thermal analysis (DTA) - within the temperature range from 40 to 120 ° C, particularly preferably within the temperature range from 45 to 110 ° C.
- DTA differential thermal analysis
- blocked polyisocyanates known for hydroxy-functional binders based on aliphatic and / or cycloaliphatic diisocyanates
- Blocked polyisocyanates are suitable any aliphatic or cycloaliphatic diisocyanates, e.g. 1,4-butane diisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), IPDI, 4,4'-diisocyanatodicyclohexylmethane, 2,4 (6) -diisocyanato-1-methylcyclohexane, 1,4-diisocyanatocyclohexane or any mixture such diisocyanates.
- BDI 1,4-butane diisocyanate
- HDI 1,6-hexamethylene diisocyanate
- IPDI 4,4'-diisocyanatodicyclohexylmethane
- 2,4 (6) -diisocyanato-1-methylcyclohexane 1,4-diisocyanatocyclohexane or any mixture such diisocyanates.
- diisocyanates with aryl structures as aliphatic or cycloaliphatic, if their isocyanate groups on alkyl or cycloalkyl carbon atoms and are not directly bound to the aromatics.
- Suitable starting diisocyanates for The production of blocked polyisocyanates is therefore also 1,3- or 1,4-bis (isocyanatomethyl) benzene or 1,3- or 1,4-bis (2-isocyanatoprop-2-yl) benzene.
- component B) present in the powder coatings according to the invention is, for example, derivatives of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane blocked with ⁇ -caprolactam (Isophorone diisocyanate; IPDI), as e.g. in DE-A 2 105 777, 2 542 191, 3 143 060, 2 735 497 and 2,842,641 describes urethanes or isocyanurates blocked with ⁇ -caprolactam of 1,4-diisocyanatocyclohexane of the type mentioned in EP-A 286 799 or simple diisocyanates blocked with ⁇ -caprolactam, e.g.
- Patent 3,857,818) 1,4-bis (isocyanatomethyl) benzene blocked with acetone oxime (US-P 4,375,539) or with diisopropyl ketoxime or diisobutyl ketoxime blocked IPDI, 4,4'-diisocyanatodicyclohexylmethane or 1,3- or 1,4-bis (2-isocyanatoprop-2-yl) benzene (EP-A 409 745) but also with triazoles (DE-A 2 812 252), cyclic amidines (DE-A 2 946 085) or secondary Amines (DE-A 3 434 881) blocked polyisocyanates suitable starting components B).
- Preferred blocked polyisocyanates B) are those based on IPDI, 4,4'-diisocyanatodicyclohexylmethane or 2,4 (6) -diisocyanato-1-methylcyclohexane with ⁇ -caprolactam as a blocking agent.
- Component B) is contained in such in the powder coating according to the invention Amounts used that on each hydroxyl group of the binder component A) 0.6 to 1.4, preferably 0.8 to 1.2, isocyanate groups of component B) omitted, the sum of in isocyanate groups of component B) in Blocking agents blocked form present isocyanate groups and free Isocyanate groups is understood.
- Suitable dicarboxylic acids C1) are, for example, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid (1,10-decanedicarboxylic acid) or hexahydrophthalic acid.
- Suitable components C2) are, for example, monomeric anhydrides of this type Dicarboxylic acids, such as succinic, glutaric or hexahydrophthalic anhydride, or polymeric anhydrides of such dicarboxylic acids, as described by receive intermolecular condensation of the acids mentioned or their mixtures can be.
- Dicarboxylic acids such as succinic, glutaric or hexahydrophthalic anhydride
- polymeric anhydrides of such dicarboxylic acids as described by receive intermolecular condensation of the acids mentioned or their mixtures can be.
- Specific examples are adipic acid (poly) anhydride, azelaic acid (poly) anhydride, Sebacic acid (poly) anhydride or dodecanedioic acid (poly) anhydride.
- the gel permeation chromatography using polystyrene as The standard molecular weight Mw of these polyanhydrides is in the generally at 1000 to 5000.
- the polyanhydrides are prepared for example by reaction of the dicarboxylic acids or the dicarboxylic acid mixtures with acetic anhydride at temperatures from 120 to 200 ° C, preferably 120 to 170 ° C.
- the acetic acid split off is, for example removed by distillation under vacuum.
- Suitable components C2) are also modified anhydrides of C1) mentioned dicarboxylic acids, for example polyol-modified polyanhydrides, such as they are accessible according to EP-A 299 420.
- polyol-modified Polyanhydrides is the molar ratio of anhydride groups to carboxyl groups generally 0.04: 1 to 5: 1, preferably 1: 1 to 3: 1
- Suitable components C2) are also polyisocyanate-modified polyanhydrides how they e.g. according to DE-A 4 427 225 by implementing Dicarboxylic acids and / or dicarboxylic acid (poly) anhydrides with any organic Polyisocyanates and, if necessary, other anhydride groups reactive compounds containing amino and / or hydroxyl groups available are.
- Suitable hydroxycarboxylic acids C3) are, in particular, those that have an intermediate 40 and 150 ° C lying melting point. These include, for example 2-hydroxyisobutyric acid (81 ° C), 2-hydroxyhexanoic acid (61 ° C), 10-hydroxydecanoic acid (76 ° C), 12-hydroxydodecanoic acid (86 ° C), 16-hydroxyhexadecanoic acid (98 ° C) and 12-hydroxyoctadecanoic acid (80 ° C).
- hydroxycarboxylic acids are generally preferred only in combination with unmodified polyanhydrides C2) in amounts of up to 50 % By weight, based on the weight of the polyanhydrides, is used.
- Component C) particularly preferably consists exclusively of at least a saturated aliphatic dicarboxylic acid with 4 to 12 carbon atoms, a monomeric or polymeric anhydride of such dicarboxylic acids or one polyanhydride modified by aliphatic and / or cycloaliphatic polyisocyanates such dicarboxylic acids.
- component D) contained in the powder coatings according to the invention is compared to carboxyl and / or carboxylic acid anhydride groups compounds of average molecular weight containing reactive groups from 200 to 5000, preferably from 200 to 2000, particularly preferably from 250 to 1000, as they are generally used as crosslinker components in powder coating technology for powder coating binders containing carboxyl groups come.
- Suitable components D) are, for example, the polyepoxides known per se, such as triglycidyl isocyanurate (TGIC) and triglycidylurazole or their Oligomers, glycidyl ethers, e.g. those based on bisphenol A, glycidyl ester, e.g. that of phthalic acid, tetrahydro- and hexahydrophthalic acid or any Mixtures of such polyepoxides.
- TGIC triglycidyl isocyanurate
- glycidylurazole Oligomers
- glycidyl ethers e.g. those based on bisphenol A
- glycidyl ester e.g. that of phthalic acid, tetrahydro- and hexahydrophthalic acid or any Mixtures of such polyepoxides.
- Suitable components D) are, for example, also ⁇ -hydroxyalkylamide groups containing compounds, such as those in EP-A 322 834 as crosslinker components are described for polyesters containing carboxyl groups.
- the production Such ⁇ -hydroxyalkylamides are generally carried out by base-catalyzed Implementation of organic polycarboxylic acid esters with ⁇ -hydroxyalkylamines Temperatures up to 200 ° C with simultaneous removal of the distillate developing alcohol.
- component D) TGIC or ⁇ -hydroxyalkylamides based on saturated dicarboxylic acid esters with 4 up to 12 carbon atoms in the dicarboxylic acid part.
- Particularly preferred Component D) consists of a ⁇ -hydroxyalkylamide, as described by Reaction of diethanolamine with a mixture of dimethyl adipate and dimethyl glutarate is obtained.
- Component D) is contained in such in the powder coating according to the invention Amounts used that 0.3 to up to each carboxyl equivalent of component C) 1.5, preferably 0.4 to 1.2, compared to carboxyl and / or carboxylic anhydride groups reactive groups of component D) are omitted, one One carboxyl group and one carboxylic anhydride group two carboxyl equivalents equivalent.
- the proportion of components C) and D) in the total amount of components A), B), C) and D) in the powder coatings according to the invention is 10 to 40 % By weight, preferably 15 to 35% by weight.
- the powder coating according to the invention can also be the usual from Powder coating technology known auxiliaries and additives E) contain.
- catalysts such as Tin (II) hexanoate, Tin (II) octanoate, tin (II) laurate, dibutyltin oxide, dibutyltin chloride, dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene or 1,8-diazabicyclo [5.4.0] -undec-7-ene.
- Catalysts come as additive E) if in general, in proportions of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on the sum of components A), B), C) and D).
- auxiliaries and additives E are, for example, leveling agents such as e.g. Polybutyl acrylate or those based on polysilicones, light stabilizers, such as. sterically hindered amines, UV absorbers, e.g. Benzotriazoles or Benzophenones and pigments such as e.g. Titanium dioxide.
- leveling agents such as e.g. Polybutyl acrylate or those based on polysilicones
- light stabilizers such as. sterically hindered amines
- UV absorbers e.g. Benzotriazoles or Benzophenones
- pigments such as e.g. Titanium dioxide.
- Additives E) include in particular color stabilizers against the Risk of overburning yellowing.
- Inert substituents trialkyl and / or triaryl phosphites such as Triethyl phosphite, triphenyl phosphite or preferably trisalkylphenyl phosphite, wherein the alkyl substituents have 6 to 12 carbon atoms.
- Trisnonylphenyl phosphite (technical product, consisting of) is very particularly preferred essentially from an ester of phosphorous acid with the adduct of tripropylene to phenol).
- components A), B), C), D) and optionally E) intimately mixed and then in the Melt combined into a homogeneous material This can be done in appropriate Units, for example heatable kneaders, but preferably by Melt extrusion take place, the extrusion temperature in general is chosen that a maximum of shear forces acts on the mixture. Around Avoid premature crosslinking of the powder coating, however an upper temperature limit of 120 ° C must not be exceeded.
- a type of production which is likewise preferred in the sense of the present invention It is also a finished powder coating, for example, in a first step only two of the individual components, for example only components B) and C), in the melt, preferably immediately after the production of one of the Components B) or C) to mix intimately with each other and only to one later, in a second step, to the resulting one, from the Components B) and C) existing storage-stable homogeneous material add other components and extrude everything together.
- the extruded mass is after cooling to room temperature and after a suitable pre-grinding to a powder coating and by sieving the grain proportions above the desired grain size, for example above 0.1 mm, free.
- the powder coating formulations prepared in this way can be prepared using customary powder application methods, such as. electrostatic powder spraying or whirl sintering the substrates to be coated are applied.
- the hardening of the coatings is carried out by heating to temperatures of 120 to 220 ° C, preferably 130 to 200 ° C, for example for a period of about 10 to 30 minutes. you receives completely matt, hard and elastic coatings, which are characterized by an excellent Characterize flow and good resistance to solvents and chemicals.
- any heat-resistant substrates such as Glass or metals are coated.
- DTA differential thermal analysis
- melt which becomes more viscous, is stirred Temperature about 3 hours after, until the content of free NCO groups less is less than 0.1% and does not decrease further.
- the melt will cool down poured a sheet, and you get a storage-stable bright solid resin with a Melting point (DTA) of approx. 55 ° C, a content of blocked NCO groups of 12.2% and of free NCO groups of 0.7%.
- DTA Melting point
- dimethyl adipate 900 parts by weight of dimethyl adipate are mixed with 100 parts by weight Dimethyl glutarate, 1460 parts by weight of diethanolamine and 5 parts by weight Potassium hydroxide mixed in a stirred vessel with distillation head and on heated to a temperature of 100 to 110 ° C.
- the resulting product distils Methanol from the reaction mixture.
- a vacuum of about 150 mbar is applied to the reaction apparatus applied, whereupon another about 100 parts by weight of methanol distill off.
- a hydroxyl-containing polyester which consists of 66.6 parts by weight Terephthalic acid, 38.2 parts by weight of neopentyl glycol, 5.3 parts by weight of 1,6-hexanediol and 4.5 parts by weight of 1,1,1-trimethylolpropane and has an OH number of 50 and a melting range (DTA) of 55 to 60 ° C, with 12.2 parts by weight of the blocked polyisocyanate B-a), accordingly an equivalent ratio of total NCO to OH of 1: 1, 7.0 parts by weight Dodecanedioic acid and 5.0 parts by weight of the ⁇ -hydroxylamide D-a), accordingly an equivalent ratio of carboxyl equivalents to carboxyl and / or Carboxylic anhydride groups reactive groups of 1: 1, 1.0 parts by weight a commercially available leveling agent based on polybutyl acrylate (Modaflow PIII®; Monsanto), 1.0 part by weight of tin (II)
- the solidified melt is made using a classifier mill ACM 2 (Hosokawa Mikropul) ground and sieved with a 90 ⁇ m sieve.
- the powder thus obtained is with an ESB cup gun at high voltage of 70 kV are sprayed onto a degreased steel sheet and 30 minutes at 180 ° C smooth, black matt coating hardened.
- the powders are blended with an ESB cup gun at a high voltage of 70 kV are sprayed onto degreased steel sheets and cured for 30 min at 180 ° C.
- the comparative examples show that the addition of only one further, for example only one carboxyl group and / or carboxylic anhydride group having component (comparative example 5) or only one opposite Carboxyl and / or carboxylic anhydride groups having reactive groups Component (comparative example 6) to one of a polyester polyol and one blocked polyisocyanate existing polyurethane system leads to coatings, that are not dull, and only moderate elasticities and durability properties exhibit.
- the powder is applied with an ESB cup gun at a high voltage of 70 kV sprayed onto a degreased steel sheet and cured at 180 ° C for 30 min.
- a black glossy lacquer film is obtained which has the following properties with a layer thickness of approx. 60 ⁇ m: ET 9.0 shine 20 ° 59 60 ° 86 Ac DH 50 judgment 2 m
- the comparative example shows that the addition of a combination of a high molecular weight Carboxylpolyester and a reactive towards carboxyl groups Crosslinker to a polyester and a blocked polyisocyanate existing polyurethane system not to a matt, but to a shiny Coating, which also has only moderate solvent resistance having.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
- E) aus der Pulverlacktechnologie bekannten Hilfs- und Zusatzstoffen,
ET | 9,0 | |
Glanz ) | 20° | 0,6 |
60° | 8,0 | |
Ac | DH | 50 |
Urteil | 0-1 1 |
Beispiel | 2 | 3 | 4 | 5 (Vergleich) | 6 (Vergleich) | |
Polyester gemäß Beispiel 1 | 37,0 | 40,6 | 38,0 | 43,4 | 44,1 | |
blockiertes Polyisocyanat | B-a) | - | - | - | 13,6 | 13,9 |
B-b) | 14,0 | - | - | - | - | |
B-c) | - | 10,4 | - | - | - | |
B-d) | - | - | 11,0 | - | - | |
Polyanhydrid | C2-a) | - | - | 9,0 | 6,0 | - |
Dodecandisäure | 7,0 | 7,0 | - | - | - | |
β-Hydroxyalkylamid | D-a) | 5,0 | 5,0 | 5,0 | - | 5,0 |
Modaflow PIII® | 1,0 | 1,0 | 1,0 | 1,0 | 1,0 | |
Zinn(II)octanoat® | 1,0 | 1,0 | 1,0 | 1,0 | 1,0 | |
Flammruß 101® | 1,1 | 1,1 | 1,1 | 1,1 | 1,1 | |
Blanc Fix M® | 33,9 | 33,9 | 33,9 | 33,9 | 33,9 |
2 | 3 | 4 | 5 (Vergleich) | 6 (Vergleich) | ||
ET | >9,0 | 9,0 | 9,0 | 1,0 | 0,5 | |
Glanz | 20° | 0,4 | 3,1 | 2,2 | 36 | 31 |
60° | 6,3 | 28 | 18 | 79 | 77 | |
Ac | DH | 50 | 50 | 50 | 50 | 50 |
Urteil | 0-1 | 1 | 1 | 2 m | 2 m |
ET | 9,0 | |
Glanz | 20° | 59 |
60° | 86 | |
Ac | DH | 50 |
Urteil | 2 m |
Claims (10)
- Pulverlack zur Herstellung matter Beschichtungen ausA) einer unterhalb von 40°C in fester und oberhalb von 130°C in flüssiger Form vorliegenden Hydroxylgruppen aufweisenden Bindemittelkomponente mit einer OH-Zahl von 25 bis 200 und einem mittleren (aus der Funktionalität und dem Hydroxylgehalt berechenbaren) Molekulargewicht von 400 bis 10000,B) einem unterhalb von 40°C in fester und oberhalb von 125°C in flüssiger Form vorliegenden blockierte und gegebenenfalls freie Isocyanatgruppen aufweisenden Polyisocyanat auf Basis aliphatischer und/oder cycloaliphatischer Diisocyanate,C) einer unterhalb von 40°C in fester und oberhalb von 160°C in flüssiger Form vorliegender Carboxyl- und/oder Carbonsäureanhydridgruppen aufweisenden Komponente, bestehend aus mindestens einer Komponente ausgewählt ausC1) aliphatischen und/oder cycloaliphatischen Dicarbonsäuren mit 4 bis 20 Kohlenstoffatomen,C2) monomeren und/oder polymeren gegebenfalls modifizierten Anhydriden derartiger Dicarbonsäuren undC3) aliphatischen Hydroxycarbonsäuren mit 4 bis 18 Kohlenstoffatomen,D) einer gegenüber Carboxyl- und/oder Carbonsäureanhydridgruppen reaktive Gruppen aufweisenden Komponente eines mittleren Molekulargewichts von 200 bis 5000,E) aus der Pulverlacktechnologie bekannten Hilfs- und Zusatzstoffen,
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente A) aus einem Hydroxylgruppen aufweisenden Polyester mit einer Erweichungstemperatur, die - bestimmt nach der Differential-Thermoanalyse (DTA) - innerhalb des Temperaturbereiches von 40 bis 120°C liegt, einer OH-Zahl von 25 bis 200 und einem mittleren (aus der Funktionalität und dem Hydroxylgehalt berechenbaren) Molekulargewicht von 1000 bis 5000 besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente B) aus einem blockierten Polyisocyanat mit einem Gehalt an blockierten Isocyanatgruppen von 8 bis 17 Gew.-% und einem Gehalt an freien Isocyanatgruppen von weniger als 1 Gew.-% besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente B) aus einem blockierte und gegebenenfalls freie Isocyanatgruppen aufweisenden Polyisocyanat auf Basis von Isophorondiisocyanat, 4,4'-Diisocyanatodicyclohexylmethan, 2,4(6)-Diisocyanato- -methylcyclohexan oder beliebigen Gemischen dieser Diisocyanate besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente C) aus mindestens einer gesättigten aliphatischen Dicarbonsäure mit 4 bis 12 Kohlenstoffatomen besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente C) aus mindestens einem monomeren oder polymeren Anhydrid einer gesättigten aliphatischen Dicarbonsäure mit 4 bis 12 Kohlenstoffatomen besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente C) aus mindestens einem Polyisocyanat-modifizierten Dicarbonsäure(poly)anhydrid auf Basis einer gesättigten aliphatischen, 4 bis 12 Kohlenstoffatome aufweisenden Dicarbonsäure mit einem Gehalt an Carboxylgruppen (berechnet als CO2H; Molekulargewicht = 45) von 0,5 bis 30 Gew.-%, einem Gehalt an Carbonsäureanhydridgruppen (berechnet als C2O3; Molekulargewicht = 72) von 5 bis 35 Gew.-% und einem Gehalt an in Amid- und/oder Harnstoffgruppen gebunden vorliegendem Stickstoff von 0,2 bis 8 Gew.-% besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente D) aus Triglycidylisocyanurat und/oder dessen Oligomeren oder einem β-Hydroxyalkylamid auf Basis gesättigter Dicarbonsäuren mit 4 bis 12 Kohlenstoffatomen besteht.
- Pulverlack gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente D) aus einem β-Hydroxyalkylamid, hergestellt durch Umsetzung von Diethanolamin mit einem Gemisch aus Adipinsäuredimethylester und Glutarsäuredimethylester, besteht.
- Verwendung des Pulverlacks gemäß Anspruch 1 zur Beschichtung beliebiger hitzeresistenter Substrate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19604581A DE19604581A1 (de) | 1996-02-08 | 1996-02-08 | Polyurethan-Pulvermattlacke |
DE19604581 | 1996-02-08 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0789043A2 EP0789043A2 (de) | 1997-08-13 |
EP0789043A3 EP0789043A3 (de) | 1998-01-14 |
EP0789043B1 true EP0789043B1 (de) | 2003-04-09 |
Family
ID=7784856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97101185A Expired - Lifetime EP0789043B1 (de) | 1996-02-08 | 1997-01-27 | Polyurethan-Pulvermattlacke |
Country Status (6)
Country | Link |
---|---|
US (1) | US5811190B1 (de) |
EP (1) | EP0789043B1 (de) |
JP (1) | JPH09227800A (de) |
CA (1) | CA2196741C (de) |
DE (2) | DE19604581A1 (de) |
TW (1) | TW341592B (de) |
Families Citing this family (12)
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CZ75298A3 (cs) * | 1996-02-29 | 1998-07-15 | Synthopol Chemie Dr. Rer. Pol. Koch Gmbh & Co. Kg | Nové polyesterpolyoly a jejich použití jako polyolových komponent v dvousložkových polyurethanových nátěrových hmotách |
DE19925543A1 (de) | 1999-06-04 | 2000-12-07 | Degussa | Urethanisierte beta-Hydroxyalkylamid-Verbindung, ein Verfahren zu ihrer Herstellung sowie deren Verwendung zur Herstellung von Pulverlacken |
DE10008928A1 (de) * | 2000-02-25 | 2001-08-30 | Degussa | Transparente oder pigmentierte Pulverlacke mit Vernetzern aus Hydroxyalkylamiden und blockierten, nicht aromatischen Polyisocyanaten |
DE10047762A1 (de) * | 2000-09-27 | 2002-04-11 | Degussa | Pulverförmige, wasserdispergierbare blockierte Polyisocyanataddukte, ein Verfahren zur Herstellung und ihre Verwendung |
US20060122357A1 (en) * | 2004-12-08 | 2006-06-08 | Thomas Faecke | Continuous method for manufacturing an acid functional blocked solid isocyanate |
US20120316290A1 (en) * | 2010-03-01 | 2012-12-13 | Lubrizol Advanced Materials, Inc. | Melt Processable Copolyurea Elastomers |
JP5999142B2 (ja) * | 2014-06-20 | 2016-09-28 | 富士ゼロックス株式会社 | 熱硬化性粉体塗料及びその製造方法、並びに塗装品及びその製造方法 |
JP6245313B2 (ja) * | 2016-05-30 | 2017-12-13 | 富士ゼロックス株式会社 | 熱硬化性粉体塗料及びその製造方法、並びに塗装品及びその製造方法 |
EP3625280B1 (de) * | 2017-05-17 | 2021-07-07 | Basf Se | Polyisocyanat (p) und verfahren zu dessen herstellung |
US10465090B2 (en) | 2017-06-22 | 2019-11-05 | Covestro Llc | Powder coating compositions with a polymeric aromatic product of an aromatic isocyanate manufacturing process |
US10400112B2 (en) | 2017-06-22 | 2019-09-03 | Covestro Llc | Powder coating compositions with a polymeric aromatic product of an aromatic isocyanate manufacturing process |
WO2019057448A1 (de) * | 2017-09-25 | 2019-03-28 | Basf Se | Zumindest teilweise blockiertes polyisocyanat (bp) |
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-
1996
- 1996-02-08 DE DE19604581A patent/DE19604581A1/de not_active Withdrawn
-
1997
- 1997-01-27 DE DE59709732T patent/DE59709732D1/de not_active Expired - Fee Related
- 1997-01-27 EP EP97101185A patent/EP0789043B1/de not_active Expired - Lifetime
- 1997-01-31 TW TW086101083A patent/TW341592B/zh active
- 1997-01-31 US US08794256 patent/US5811190B1/en not_active Expired - Fee Related
- 1997-02-04 CA CA002196741A patent/CA2196741C/en not_active Expired - Fee Related
- 1997-02-06 JP JP9036897A patent/JPH09227800A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
CA2196741A1 (en) | 1997-08-09 |
EP0789043A3 (de) | 1998-01-14 |
DE59709732D1 (de) | 2003-05-15 |
US5811190A (en) | 1998-09-22 |
US5811190B1 (en) | 2000-03-14 |
EP0789043A2 (de) | 1997-08-13 |
DE19604581A1 (de) | 1997-08-14 |
TW341592B (en) | 1998-10-01 |
CA2196741C (en) | 2005-10-18 |
JPH09227800A (ja) | 1997-09-02 |
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